Organic electroluminescent device emitting blue light

ABSTRACT

The present invention relates to a an organic electroluminescent device comprising a light-emitting layer B comprising a host material HB, a first thermally activated delayed fluorescence (TADF) material EB, and a second TADF material SB, wherein EB transfers energy to SB and SB emits TADF with an emission maximum between 420 and 500 nm.

The present invention relates to organic electroluminescent devicescomprising a light-emitting layer B comprising a host material H^(B), afirst thermally activated delayed fluorescence (TADF) material E^(B),and a second TADF material S^(B), wherein E^(B) transfers energy toS^(B), and S^(B) emits TADF with an emission maximum between 420 and 500nm.

DESCRIPTION

Organic electroluminescent devices containing one or more light-emittinglayers based on organics such as, e.g., organic light emitting diodes(OLEDs), light emitting electrochemical cells (LECs) and light-emittingtransistors gain increasing importance. In particular, OLEDs arepromising devices for electronic products such as e.g. screens, displaysand illumination devices. In contrast to most electroluminescent devicesessentially based on inorganics, organic electroluminescent devicesbased on organics are often rather flexible and producible inparticularly thin layers. The OLED-based screens and displays alreadyavailable today bear particularly beneficial brilliant colors, contrastsand are comparably efficient with respect to their energy consumption.

A central element of an organic electroluminescent device for generatinglight is a light-emitting layer placed between an anode and a cathode.When a voltage (and current) is applied to an organic electroluminescentdevice, holes and electrons are injected from an anode and a cathode,respectively, to the light-emitting layer. Typically, a hole transportlayer is located between light-emitting layer and the anode, and anelectron transport layer is located between light-emitting layer and thecathode. The different layers are sequentially disposed. Excitons ofhigh energy are then generated by recombination of the holes and theelectrons. The decay of such excited states (e.g., singlet states suchas S1 and/or triplet states such as T1) to the ground state (S0)desirably leads to light emission.

In order to enable efficient energy transport and emission, an organicelectroluminescent device comprises one or more host compounds and oneor more emitter compounds as dopants. Challenges when generating organicelectroluminescent devices are thus the improvement of the illuminationlevel of the devices (i.e., brightness per current), obtaining a desiredlight spectrum and achieving suitable (long) lifespans.

There is still a lack of efficient and stable OLEDs that emit in thedeep blue region of the visible light spectrum, which would be expressedby a small CIE_(y) value. Accordingly, there is still the unmettechnical need for organic electroluminescent devices which have a longlifetime and high quantum yields, in particular in the deep blue range.

Surprisingly, it has been found that an organic electroluminescentdevice's light-emitting layer comprising two thermally activated delayedfluorescence (TADF) materials and a host material provides an organicelectroluminescent device having good lifetime and quantum yields andexhibiting deep blue emission. Herein, one of the TADF materials, inparticular the one having a higher singlet state energy level, transfersenergy to the other TADF material, in particular having a lower singletstate energy level, which bears an emission maximum between 420 and 500nm. Surprisingly, devices either show an emission at a lower wavelength,longer lifetime and/or higher efficiencies than devices comprising onlyone of the two TADF materials in the light-emitting layer.

Accordingly, one aspect of the present invention relates to an organicelectroluminescent device which comprises a light-emitting layer Bcomprising:

-   -   (i) a host material H^(B), which has a lowermost excited singlet        state energy level S1^(H) and a lowermost excited triplet state        energy level T1^(H),    -   (ii) a first thermally activated delayed fluorescence (TADF)        material E^(B), which has a lowermost excited singlet state        energy level S1^(E) and a lowermost excited triplet state energy        level T1^(E); and    -   (iii) a second TADF material 5B, which has a lowermost excited        singlet state energy level S1^(S) and a lowermost excited        triplet state energy level T1^(S), wherein E^(B) transfers        energy to S^(B) and S^(B) emits thermally activated delayed        fluorescence with an emission maximum between 420 and 500 nm;        and wherein the relations expressed by the following        formulas (1) to (4) apply:        S1^(H) >S1^(E)  (1)        S1^(H) >S1^(S)  (2)        S1^(E) >S1^(S)  (3)        T1^(H) >T1^(S)  (4).

According to the invention, the lowermost excited singlet state of thehost material H^(B) is higher in energy than the lowermost excitedsinglet state of the first thermally activated delayed fluorescence(TADF) material E^(B). The lowermost excited singlet state of the hostmaterial H^(B) is higher in energy than the lowermost excited singletstate of the second TADF material S^(B). The lowermost excited singletstate of the first TADF material E^(B) is higher in energy than thelowermost excited singlet state of the second TADF material S^(B). Thelowermost excited triplet state of the host material H^(B) is higher inenergy than the lowermost excited triplet state of the second TADFmaterial S^(B).

As used herein, the terms “TADF material” and “TADF emitter” may beunderstood interchangeably. When one of the terms “emitter” “emittercompound” or the like is used, this may be understood in that preferablya TADF material of the present invention is meant, in particular one orthose designated as E^(B) and S^(B), respectively.

In a preferred embodiment, the lowermost excited triplet state of thehost material H^(B) is higher in energy than the lowermost excitedtriplet state of the first TADF material E^(B): T1^(H)>T1^(E).

Alternatively, the lowermost excited triplet state of the host materialH^(B) may be lower in energy than the lowermost excited triplet state ofthe first TADF material E^(B): T1^(H)<T1^(E).

In a preferred embodiment, the lowermost excited triplet state of thefirst TADF material E^(B) is higher in energy than the lowermost excitedtriplet state of the second TADF material S^(B): T1^(E)>T1^(S).

In a preferred embodiment, the following relation applyS1^(E)>S1^(S)≥T1^(e)>T1^(S) and S1^(E)-T1^(S)≤0.4 eV. In other words,the lowermost excited singlet state of the first TADF material E^(B) ishigher in energy than lowermost excited singlet state of the second TADFmaterial S^(B), which is at least equal to or higher in energy than orequal in energy with the lowermost excited triplet state of the firstTADF material E^(B), which is higher in energy than the lowermostexcited triplet state of second TADF material S^(B). In a preferredembodiment, all four states are within a range (i.e., difference inenergy) of 0.4 eV or less, preferably in a range of 0.3 eV or less,particular in a range of 0.2 eV or less.

Due to the low energy difference between the lowermost excited singletand triplet states of the TADF materials E^(B) and S^(B) excitontransfer between different states of E^(B) and S^(B) is sufficientlyenabled. In addition, transfers between states of differentmultiplicities may be enabled due to the low energy difference.

This may include energy transfer

(a) from a singlet state of one TADF material to the singlet state ofthe other TADF material,

(b) from a triplet state of one TADF material to the triplet state ofthe other TADF material,

(c) from a singlet state of one TADF material to the triplet state ofthe other TADF material, and/or

(d) from a triplet state of one TADF material to the singlet state ofthe other TADF material.

Interestingly, in a variety of combinations of E^(B) and S^(B) of thepresent invention, energy transfer may also occur to higher as well aslower energy levels, such as exemplarily:

(a) from T1^(S) to S1^(E),

(b) from S1^(S) to T1^(E),

(c) from T1^(E) to S1^(S),

(d) from S1^(E) to T1^(S),

(e) from S1^(S) to S1^(E),

(f) from S1^(E) to S1^(S),

(g) from T1^(S) to T1^(E), and/or

(h) from T1^(E) to T1^(S).

Surprisingly it was found, that the main contribution to the emissionband of the optoelectronic device according to the invention can beattributed to the emission of S^(B) indicating a sufficient transfer ofenergy from E^(B) to S^(B).

The emission of the device according to the invention typically appearsblue-shifted compared to devices with similar device architecture and anemission layer comprising the TADF material S^(B) as emitter and/or showlonger lifetimes and/or higher efficiencies.

The emission of the device according to the invention show longerlifetimes and/or higher efficiencies compared to devices with similardevice architecture and an emission layer comprising the TADF materialE^(B), while the emission appears at similar colors or evenblue-shifted.

Particularly interesting is that, depending on the combinations of E^(B)and S^(B) of the present invention, energy from lower energy states canalso be transferred to higher energy states of the other compound. Alsotaking the reversed intersystem crossing (RISC) occurring in TADFemitters into account, the combinations of E^(B) and S^(B) of thepresent invention may lead to particularly high emission of the TADFmaterial S^(B).

According to the present invention, a TADF material is characterized inthat it exhibits a ΔE_(ST) value, which corresponds to the energydifference between the lowermost excited singlet state (S1) and thelowermost excited triplet state (T1), of less than 0.4 eV, preferablyless than 0.3 eV, more preferably less than 0.2 eV, even more preferablyless than 0.1 eV or even less than 0.05 eV.

As used herein, the terms organic electroluminescent device andopto-electronic light-emitting devices may be understood in the broadestsense as any device comprising a light-emitting layer B comprising ahost material H^(B), a first TADF material E^(B) and a second TADFmaterial S^(B).

The organic electroluminescent device may be understood in the broadestsense as any device based on organic materials that is suitable foremitting light in the visible or nearest ultraviolet (UV) range, i.e.,in the range of a wavelength of from 380 to 800 nm. More preferably,organic electroluminescent device may be able to emit light in thevisible range, i.e., of from 400 to 800 nm.

In a preferred embodiment, the organic electroluminescent device is adevice selected from the group consisting of an organic light emittingdiode (OLED), a light emitting electrochemical cell (LEC), and alight-emitting transistor.

Particularly preferably, the organic electroluminescent device is anorganic light emitting diode (OLED). Optionally, the organicelectroluminescent device as a whole may be intransparent,semi-transparent or (essentially) transparent.

The term “layer” as used in the context of the present inventionpreferably is a body that bears an extensively planar geometry.

The light-emitting layer B preferably bears a thickness of not more than1 mm, more preferably not more than 0.1 mm, even more preferably notmore than 10 μm, even more preferably not more than 1 μm, in particularnot more than 0.1 μm.

In a preferred embodiment, the first thermally activated delayedfluorescence (TADF) material E^(B) is an organic TADF emitter. Accordingto the invention, organic emitter or organic material means that theemitter or material (predominantly) consists of the elements hydrogen,carbon, nitrogen, and optionally fluorine and optionally oxygen.Particularly preferably, it does not contain any transition metals.

In a preferred embodiment, the first TADF material E^(B) is an organicTADF emitter. In a preferred embodiment, the second TADF material S^(B)is an organic TADF emitter. In a more preferred embodiment, the firstTADF material E^(B) and the second TADF material S^(B) are both organicTADF emitters.

In a particularly preferred embodiment, the at least one TADF materialE^(B) is a blue TADF emitter, preferably a deep-blue TADF emitter.

The person skilled in the art will notice that the light-emitting layerB will typically be incorporated in the organic electroluminescentdevice of the present invention. Preferably, such organicelectroluminescent device comprises at least the following layers: atleast one light-emitting layer B, at least one anode layer A and atleast one cathode layer C.

Preferably, the anode layer A contains at least one component selectedfrom the group consisting of indium tin oxide, indium zinc oxide, PbO,SnO, graphite, doped silicium, doped germanium, doped GaAs, dopedpolyaniline, doped polypyrrole, doped polythiophene, and mixtures of twoor more thereof.

Preferably, the cathode layer C contains at least one component selectedfrom the group consisting of Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, In, W,Pd, LiF, Ca, Ba, Mg, and mixtures or alloys of two or more thereof.

Preferably, the light-emitting layer B is located between an anode layerA and a cathode layer C. Accordingly, the general set-up is preferablyA-B-C. This does of course not exclude the presence of one or moreoptional further layers. These can be present at each side of A, of Band/or of C.

In a preferred embodiment, the organic electroluminescent devicecomprises at least the following layers:

-   A) an anode layer A containing at least one component selected from    the group consisting of indium tin oxide, indium zinc oxide, PbO,    SnO, graphite, doped silicium, doped germanium, doped GaAs, doped    polyaniline, doped polypyrrole, doped polythiophene, and mixtures of    two or more thereof;-   B) the light-emitting layer B; and-   C) a cathode layer C containing at least one component selected from    the group consisting of Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, In, W,    Pd, LiF, Ca, Ba, Mg, and mixtures or alloys of two or more thereof,

wherein the light-emitting layer B is located between the anode layer Aand the a cathode layer C.

In one embodiment, when the organic electroluminescent device is anOLED, it may optionally comprise the following layer structure:

-   A) an anode layer A, exemplarily comprising indium tin oxide (ITO);    HTL) a hole transport layer HTL;-   B) a light-emitting layer B according to present invention as    described herein; ETL) an electron transport layer ETL; and-   C) a cathode layer, exemplarily comprising Al, Ca and/or Mg.

Preferably, the order of the layers herein is A-HTL-B-ETL-C.

Furthermore, the organic electroluminescent device may optionallycomprise one or more protective layers protecting the device fromdamaging exposure to harmful species in the environment including,exemplarily moisture, vapor and/or gases.

Preferably, the anode layer A is located on the surface of a substrate.The substrate may be formed by any material or composition of materials.Most frequently, glass slides are used as substrates. Alternatively,thin metal layers (e.g., copper, gold, silver or aluminum films) orplastic films or slides may be used. This may allow a higher degree offlexibility. The anode layer A is mostly composed of materials allowingto obtain an (essentially) transparent film. As at least one of bothelectrodes should be (essentially) transparent in order to allow lightemission from the OLED, either the anode layer A or the cathode layer Ctransparent. Preferably, the anode layer A comprises a large content oreven consists of transparent conductive oxides (TCOs).

Such anode layer A may exemplarily comprise indium tin oxide, aluminumzinc oxide, fluor tin oxide, indium zinc oxide, PbO, SnO, zirconiumoxide, molybdenum oxide, vanadium oxide, wolfram oxide, graphite, dopedSi, doped Ge, doped GaAs, doped polyaniline, doped polypyrrol and/ordoped polythiophene.

Particularly preferably, the anode layer A (essentially) consists ofindium tin oxide (ITO) (e.g., (InO₃)_(0.9)(SnO₂)_(0.1)). The roughnessof the anode layer A caused by the transparent conductive oxides (TCOs)may be compensated by using a hole injection layer (HIL). Further, theHIL may facilitate the injection of quasi charge carriers (i.e., holes)in that the transport of the quasi charge carriers from the TCO to thehole transport layer (HTL) is facilitated. The hole injection layer(HIL) may comprise poly-3,4-ethylendioxy thiophene (PEDOT), polystyrenesulfonate (PSS), MoO₂, V₂O₅, CuPC or Cul, in particular a mixture ofPEDOT and PSS. The hole injection layer (HIL) may also prevent thediffusion of metals from the anode layer A into the hole transport layer(HTL). The HIL may exemplarily comprise PEDOT:PSS (poly-3,4-ethylendioxythiophene: polystyrene sulfonate), PEDOT (poly-3,4-ethylendioxythiophene), mMTDATA (4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine),Spiro-TAD (2,2′,7,7′-tetrakis(n,n-diphenylamino)-9,9′-spirobifluorene),DNTPD(N1,N1′-(biphenyl-4,4′-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-diamine),NPB(N,N′-nis-(1-naphthalenyl)-N,N′-bis-phenyl-(1,1′-biphenyl)-4,4′-diamine),NPNPB (N,N′-diphenyl-N,N′-di-[4-(N,N-diphenyl-amino)phenyl]benzidine),MeO-TPD (N,N,N′, N′-tetrakis(4-methoxyphenyl)-benzidine), HAT-CN(1,4,5,8,9,11-hexaazatriphenylen-hexacarbonitrile) and/or Spiro-NPD(N,N′-diphenyl-N,N′-bis-(1-naphthyl)-9,9′-spirobifluorene-2,7-diamine).

Adjacent to the anode layer A or hole injection layer (HIL) typically ahole transport layer (HTL) is located. Herein, any hole transportcompound may be used. Exemplarily, electron-rich heteroaromaticcompounds such as triarylamines and/or carbazoles may be used as holetransport compound. The HTL may decrease the energy barrier between theanode layer A and the light-emitting layer B (serving as emitting layer(EML)). The hole transport layer (HTL) may also be an electron blockinglayer (EBL). Preferably, hole transport compounds bear comparably highenergy levels of their triplet states T1. Exemplarily the hole transportlayer (HTL) may comprise a star-shaped heterocycle such astris(4-carbazoyl-9-ylphenyl)amine (TCTA), poly-TPD(poly(4-butylphenyl-diphenyl-amine)), [alpha]-NPD(poly(4-butylphenyl-diphenyl-amine)), TAPC(4,4′-cyclohexyliden-bis[N,N-bis(4-methylphenyl)benzenamine]), 2-TNATA(4,4′,4″-tris[2-naphthyl(phenyl)-amino]triphenylamine), Spiro-TAD,DNTPD, NPB, NPNPB, MeO-TPD, HAT-CN and/or TrisPcz(9,9′-diphenyl-6-(9-phenyl-9H-carbazol-3-yl)-9H,9′H-3,3′-bicarbazole).In addition, the HTL may comprise a p-doped layer, which may be composedof an inorganic or organic dopant in an organic hole-transportingmatrix. Transition metal oxides such as vanadium oxide, molybdenum oxideor tungsten oxide may exemplarily be used as inorganic dopant.

Tetrafluorotetracyanoquinodimethane (F4-TCNQ),copper-pentafluorobenzoate (Cu(I)pFBz) or transition metal complexes mayexemplarily be used as organic dopant.

The EBL may exemplarily comprise mCP (1,3-bis(carbazol-9-yl)benzene),TCTA, 2-TNATA, mCBP (3,3-di(9H-carbazol-9-yl)biphenyl),9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole,9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole,9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole,9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole,9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, tris-Pcz, CzSi(9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole), and/orDCB (N,N′-dicarbazolyl-1,4-dimethylbenzene).

According to the invention, the emission layer B comprises at least onehost material H^(B), the first TADF material E^(B) and the second TADFmaterial S^(B).

In a preferred embodiment of the invention, the light-emitting layer Bcomprises:

-   (i) 5-98%, more preferably 50-92%, even more preferably 70-85% by    weight of the host compound H^(B);-   (ii) 1-50%, more preferably 5-35%, even more preferably 10-20% by    weight of the first TADF material E^(B); and-   (iii) 1-50%, more preferably 3-15%, even more preferably 5-10% by    weight of the second TADF material S^(B), and optionally-   (iv) 0-93% by weight of one or more further host compounds H^(B2)    differing from H^(B); and optionally-   (v) 0-93% by weight of one or more solvents.

Exemplarily, the host material H^(B) and/or the optionally presentfurther host compound H^(B2) may be selected from the group consistingof CBP (4,4′-Bis-(N-carbazolyl)-biphenyl), mCP, mCBP Sif87(dibenzo[b,d]thiophen-2-yltriphenylsilane), CzSi, Sif88(dibenzo[b,d]thiophen-2-yl)diphenylsilane), DPEPO(bis[2-(diphenylphosphino)phenyl] ether oxide),9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole,9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole,9-[3-(dibenzothio-phen-2-yl)phenyl]-9H-carbazole,9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole,9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, T2T(2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T(2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine) and/or TST(2,4,6-tris(9,9′-spirobifluorene-2-yl)-1,3,5-triazine). In oneembodiment of the invention, the emission layer B comprises a so-calledmixed-host system with at least one hole-dominant (n-type) host and oneelectron-dominant (p-type) host.

In one embodiment, the emission layer B comprises the first TADFmaterial E^(B) and the second TADF material S^(B), and hole-dominanthost H^(B) selected from the group consisting of CBP, mCP, mCBP,9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole,9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole,9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole and9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole.

In a preferred embodiment, the first TADF material E^(B) has a highestoccupied molecular orbital HOMO(E^(B)) having an energy E^(HOMO)(E^(B))and the host compound H^(B) has a highest occupied molecular orbitalHOMO(H^(B)) having an energy E^(Homo)(H^(B)) whereinE^(HOMO)(E^(B))−E^(HOMO)(H^(B))≤0.3 eV andE^(HOMO)(E^(B))−E^(HOMO)(E^(B))≥0.3 eV. In other words, the HOMO(H^(B))of the host H^(B) can be higher or lower in energy compared to theHOMO(E^(B)) of the first TADF material E^(B), but the difference doesnot exceed 0.3 eV, more preferably does not exceed 0.2 eV.

In a preferred embodiment, the second TADF material S^(B) has a highestoccupied molecular orbital HOMO(S^(B)) having an energy E^(HOMO)(S^(B))and the host compound H^(B) has a highest occupied molecular orbitalHOMO(H^(B)) having an energy E^(HOMO)(H^(B)), whereinE^(HOMO)(S^(B))−E^(HOMO)(H^(B))≤0.3 eV andE^(HOMO)(S^(B))−E^(HOMO)(H^(B))≥−0.3 eV. In other word, the HOMO(H^(B))of the host H^(B) can be higher or lower in energy compared to theHOMO(S^(B)) of the second TADF material S^(B), but the difference doesnot exceed 0.4 eV, preferably 0.3 eV, more preferably does not exceed0.2 eV.

In a further preferred embodiment, the first TADF material E^(B) has ahighest occupied molecular orbital HOMO(E^(B)) having an energyE^(HOMO)(E^(B)), the second TADF material S^(B) has a highest occupiedmolecular orbital HOMO(S^(B)) having an energy EH^(OMO)(S^(B))) and thehost compound H^(B) has a highest occupied molecular orbital HOMO(H^(B))having an energy E^(HOMO)(H^(B)), whereinE^(HOMO)(H^(B))≥E^(HOMO)(S^(B))≥E^(HOMO)(E^(B)).

In a further embodiment, the first TADF material E^(B) has a highestoccupied molecular orbital HOMO(E^(B)) having an energy E^(HOMO)(E^(B)),the second TADF material S^(B) has a highest occupied molecular orbitalHOMO(S^(B)) having an energy E^(HOMO)(S^(B)) and the host compound H^(B)has a highest occupied molecular orbital HOMO(H^(B)) having an energyE^(HOMO)(H^(B)), whereinE^(HOMO)(H^(B))>E^(HOMO)(S^(B))>E^(HOMO)(E^(B)). In this embodiment, thehost significantly participates in the hole-transport.

In a further embodiment, the first TADF material E^(B) has a highestoccupied molecular orbital HOMO(E^(B)) having an energy E^(HOMO)(E^(B)),the second TADF material S^(B) has a highest occupied molecular orbitalHOMO(S^(B)) having an energy E^(HOMO)(S^(B)) and the host compound H^(B)has a highest occupied molecular orbital HOMO(H^(B)) having an energyE^(HOMO)(H^(B)), whereinE^(HOMO)(H^(B))≥E^(HOMO)(E^(B))≥E^(HOMO)(S^(B)).

In a further embodiment, the first TADF material E^(B) has a highestoccupied molecular orbital HOMO(E^(B)) having an energy E^(HOMO)(E^(B)),the second TADF material S^(B) has a highest occupied molecular orbitalHOMO(S^(B)) having an energy E^(HOMO)(S^(B)) and the host compound H^(B)has a highest occupied molecular orbital HOMO(H^(B)) having an energyE^(HOMO)(H^(B)), whereinE^(HOMO)(H^(B))>E^(HOMO)(E^(B))>E^(HOMO)(S^(B)). In this embodiment, thehost significantly participates in the hole-transport.

In another embodiment, the first TADF material E^(B) has a lowestunoccupied molecular orbital LUMO(E^(B)) having an energy E^(LUMO)E^(B))and the host compound H^(B) has a lowest unoccupied molecular orbitalLUMO(H^(B)) having an energy E^(LUMO)(H^(B)), whereinE^(LUMO)(E^(B))−E^(LUMO)(H^(B))≤0.3 eV andE^(LUMO)(E^(B))−E^(LUMO)(H^(B))≥−0.3 eV. In other word, the LUMO(H^(B))of the host H^(B) can be higher or lower in energy compared to theLUMO(E^(B)) of the first TADF material E^(B), but the difference doesnot exceed 0.3 eV, more preferably does not exceed 0.2 eV.

In a further embodiment, the second TADF material S^(B) has a lowestunoccupied molecular orbital LUMO(S^(B)) having an energyE^(LUMO)(S^(B)) and the host compound H^(B) has a lowest unoccupiedmolecular orbital LUMO(H^(B)) having an energy E^(LUMO)(H^(B)), whereinE^(LUMO)(S^(B))−E^(LUMO)(H^(B))≤0.3 eV andE^(LUMO)(S^(B))−E^(LUMO)(H^(B))≥−0.3 eV. In other word, the LUMO(H^(B))of the host H^(B) can be higher or lower in energy compared to theLUMO(S^(B)) of the second TADF material S^(B), but the difference doesnot exceed 0.3 eV, more preferably does not exceed 0.2 eV.

In a further embodiment, the first TADF material E^(B) has a lowestunoccupied molecular orbital LUMO(E^(B)) having an energyE^(LUMO)(E^(B)), the second TADF material S^(B) has a lowest unoccupiedmolecular orbital LUMO(S^(B)) having an energy E^(LUMO)(S^(B)) and thehost compound H^(B) has a lowest unoccupied molecular orbitalLUMO(H^(B)) having an energy E^(LUMO)(H^(B)), wherein E^(LUMO)(H^(B))E^(LUMO)(S^(B)) E^(LUMO)(E^(B)).

In a further embodiment, the first TADF material E^(B) has a lowestunoccupied molecular orbital LUMO(E^(B)) having an energyE^(LUMO)(E^(B)), the second TADF material S^(B) has a lowest unoccupiedmolecular orbital LUMO(S^(B)) having an energy E^(LUMO)(S^(B)) and thehost compound H^(B) has a lowest unoccupied molecular orbitalLUMO(H^(B)) having an energy E^(LUMO)(H^(B)), whereinE^(LUMO)(H^(B))≤E^(LUMO)(S^(B))≤E^(LUMO)(E^(B)).

In this embodiment, the host significantly participates in theelectron-transport.

In a further embodiment, the first TADF material E^(B) has a lowestunoccupied molecular orbital LUMO(E^(B)) having an energyE^(LUMO)(E^(B)), the second TADF material S^(B) has a lowest unoccupiedmolecular orbital LUMO(S^(B)) having an energy E^(LUMO)(S^(B)) and thehost compound H^(B) has a lowest unoccupied molecular orbitalLUMO(H^(B)) having an energy E^(LUMO)(H^(B)), wherein E^(LUMO)(H^(B))E^(LUMO)(E^(B)) E^(LUMO)(S^(B)).

In a further embodiment, the first TADF material E^(B) has a lowestunoccupied molecular orbital LUMO(E^(B)) having an energyE^(LUMO)(E^(B)), the second TADF material S^(B) has a lowest unoccupiedmolecular orbital LUMO(S^(B)) having an energy E^(LUMO)(S^(B)) and thehost compound H^(B) has a lowest unoccupied molecular orbitalLUMO(H^(B)) having an energy E^(LUMO)(H^(B)), whereinE^(LUMO)(H^(B))<E^(LUMO)(E^(B))<E^(LUMO)(S^(B)). In this embodiment, thehost significantly participates in the electron-transport.

In a further embodiment, the emission layer B comprises the first TADFmaterial E^(B) having a highest occupied molecular orbital HOMO(E^(B))having an energy E^(HOMO)(E^(B))) and a lowest unoccupied molecularorbital LUMO(E^(B)) having an energy E^(LUMO)(E^(B)) the second TADFmaterial S^(B) having a highest occupied molecular orbital HOMO(S^(B))having an energy E^(HOMO)(S^(B)) and a lowest unoccupied molecularorbital LUMO(S^(B)) having an energy E^(LUMO)(S^(B)), the host compoundH^(B) having a highest occupied molecular orbital HOMO(H^(B)) having anenergy E^(HOMO)(H^(B)) and a lowest unoccupied molecular orbitalLUMO(H^(B)) having an energy E^(LUMO)(H^(B)) and a further host compoundH^(B2) having a highest occupied molecular orbital HOMO(H^(B2)) havingan energy EH^(OMO)(H^(B2))) and a lowest unoccupied molecular orbitalLUMO(H^(B2)) having an energy E^(LUMO)(H^(B2)), wherein

E^(HOMO)(E^(B))−E^(HOMO)(H^(B))≤0.3 eV andE^(HOMO)(E^(B))−E^(HOMO)(H^(B))≥−0.3 eV; and

E^(LUMO)(E^(B))−E^(LUMO)(H^(B2))≤0.3 eV andE^(LUMO)(E^(B))−E^(LUMO)(H^(B2))≥−0.3 eV; and optionally

E^(HOMO)(S^(B))−E^(HOMO)(H^(B))≤0.3 eV andE^(HOMO)(S^(B))−E^(HOMO)(H^(B))≥−0.3 eV; and optionally

E^(LUMO)(E^(B))−E^(LUMO)(H^(B2))≤0.3 eV andE^(LUMO)(E^(B))−E^(LUMO)(H^(B2))≥−0.3 eV;

In a preferred embodiment, the emission layer B comprises the first TADFmaterial E^(B) and the second TADF material S^(B), a mixed-host systemcomprising T2T as electron-dominant host H^(B2) and a host H^(B)selected from the group consisting of CBP, mCP, mCBP,9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole,9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole,9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole,9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole and9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole as hole-dominanthost.

Orbital and excited state energies can be determined either by means ofexperimental methods known to the person skilled in the art.Experimentally, the energy of the highest occupied molecular orbitalE^(HOMO) is determined by methods known to the person skilled in the artfrom cyclic voltammetry measurements with an accuracy of 0.1 eV. Theenergy of the lowest unoccupied molecular orbital E^(LUMO) is calculatedas E^(HOMO)+E^(gap), where E^(gap) is determined as follows: For hostcompounds, the onset of emission of a film with 10% by weight of host inpoly(methyl methacrylate) (PMMA) is used as E^(gap), unless statedotherwise. For emitter compounds, E^(gap) is determined as the energy atwhich the excitation and emission spectra of a film with 10% by weightof emitter in PMMA cross.

The energy of the first excited triplet state T1 is determined from theonset of emission at low temperature, typically at 77 K. For hostcompounds, where the first excited singlet state and the lowest tripletstate are energetically separated by >0.4 eV, the phosphorescence isusually visible in steady-state spectra in 2-Me-THF. The triplet energycan thus be determined as the onset of the phosphorescence spectra. ForTADF emitter compounds, the energy of the first excited triplet state T1is determined from the onset of the delayed emission spectrum at 77 K,if not otherwise stated measured in a film of poly(methyl methacrylate)(PMMA) with 10% by weight of emitter. Both for host and emittercompounds, the energy of the first excited singlet state S1 isdetermined from the onset of the emission spectrum, if not otherwisestated, measured in a film of poly(methyl methacrylate) (PMMA) with 10%by weight of the respective host or emitter compound. Typically, thiscomposition does not comprise further host or emitter compounds besidethe one investigated.

In the electron transport layer (ETL, any electron transporter may beused. Exemplarily, compounds poor of electrons such as, e.g.,benzimidazoles, pyridines, triazoles, oxadiazoles (e.g.,1,3,4-oxadiazole), phosphinoxides and sulfone, may be used. Exemplarily,an electron transporter ETM^(D) may also be a star-shaped heterocyclesuch as 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi). TheETM^(D) may exemplarily be NBphen(2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3(Aluminum-tris(8-hydroxyquinoline)), TSPO1(diphenyl-4-triphenylsilylphenyl-phosphinoxide), BPyTP2(2,7-di(2,2′-bipyridin-5-yl)triphenyle), Sif87(dibenzo[b,d]thiophen-2-yltriphenylsilane), Sif88(dibenzo[b,d]thiophen-2-yl)diphenylsilane), BmPyPhB(1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene) and/or BTB(4,4′-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1′-biphenyl). Optionally,the electron transport layer may be doped with materials such as Liq(8-hydroxyquinolinolatolithium). Optionally, a second electron transportlayer may be located between electron transport layer and the cathodelayer C.

Adjacent to the electron transport layer (ETL), a cathode layer C may belocated. Exemplarily, the cathode layer C may comprise or may consist ofa metal (e.g., Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, LiF, Ca, Ba, Mg, In,W, or Pd) or a metal alloy. For practical reasons, the cathode layer Cmay also consist of (essentially) intransparent metals such as Mg, Ca orAl. Alternatively or additionally, the cathode layer C may also comprisegraphite and or carbon nanotubes (CNTs). Alternatively, the cathodelayer C may also consist of nanoscale silver wires.

An OLED may further, optionally, comprise a protection layer between theelectron transport layer (ETL) D and the cathode layer C (which may bedesignated as electron injection layer (EIL)). This layer may compriselithium fluoride, caesium fluoride, silver, Liq(8-hydroxyquinolinolatolithium), Li₂O, BaF₂, MgO and/or NaF. As usedherein, if not defined more specifically in a particular context, thedesignation of the colors of emitted and/or absorbed light is asfollows:

violet: wavelength range of >380-420 nm;

deep blue: wavelength range of >420-470 nm;

sky blue: wavelength range of >470-500 nm;

green: wavelength range of >500-560 nm;

yellow: wavelength range of >560-580 nm;

orange: wavelength range of >580-620 nm;

red: wavelength range of >620-800 nm.

With respect to emitter compounds, such colors refer to the emissionmaximum λ_(max) ^(PMMA) of a poly(methyl methacrylate) (PMMA) film with10% by weight of the emitter. Therefore, exemplarily, a deep blueemitter has an emission maximum λ_(max) ^(PMMA) in the range of from 420to 470 nm, a sky blue emitter has an emission maximum λ_(max) ^(PMMA) inthe range of from 470 to 500 nm, a green emitter has an emission maximumλ_(max) ^(PMMA) in a range of from 500 to 560 nm, a red emitter has anemission maximum λ_(max) ^(PMMA) in a range of from 620 to 800 nm.

A deep blue emitter may preferably have an emission maximum λ_(max)^(PMMA) of below 475 nm, more preferably below 470 nm, even morepreferably below 465 nm or even below 460 nm. It will typically be above420 nm, preferably above 430 nm, more preferably above 440 nm.

Accordingly, a further embodiment of the present invention relates to anOLED, which exhibits an external quantum efficiency at 1000 cd/m² ofmore than 10%, more preferably of more than 12%, more preferably of morethan 15%, even more preferably of more than 17% or even more than 20%and/or exhibits an emission maximum between 420 nm and 500 nm,preferably between 430 nm and 490 nm, more preferably between 440 nm and480 nm, even more preferably between 450 nm and 470 nm and/or exhibits aLT80 value at 500 cd/m² of more than 100 h, preferably more than 200 h,more preferably more than 400 h, even more preferably more than 750 h oreven more than 1000 h.

A further embodiment of the present invention relates to an OLED, whichemits light at a distinct color point. According to the presentinvention, the OLED emits light with a narrow emission band (small fullwidth at half maximum (FWHM)). In a preferred embodiment, the OLEDaccording to the invention emits light with a FWHM of the main emissionpeak of below 0.50 eV, more preferably of below 0.46 eV, even morepreferably of below 0.43 eV or even below 0.41 eV.

A further aspect of the present invention relates to an OLED, whichemits light with CIEx and CIEy color coordinates close to the CIEx(=0.131) and CIEy (=0.046) color coordinates of the primary color blue(CIEx=0.131 and CIEy=0.046) as defined by ITU-R Recommendation BT.2020(Rec. 2020) and thus is suited for the use in Ultra High Definition(UHD) displays, e.g. UHD-TVs. In commercial applications, typicallytop-emitting (top-electrode is transparent) devices are used, whereastest devices as used throughout the present application representbottom-emitting devices (bottom-electrode and substrate aretransparent). The CIEy color coordinate of a blue device can be reducedby up to a factor of two, when changing from a bottom- to a top-emittingdevice, while the CIEx remains nearly unchanged (Okinaka et al.doi:10.1002/sdtp.10480). Accordingly, a further aspect of the presentinvention relates to an OLED, whose emission exhibits a CIEx colorcoordinate of between 0.02 and 0.30, preferably between 0.03 and 0.25,more preferably between 0.05 and 0.20 or even more preferably between0.08 and 0.18 or even between 0.10 and 0.15 and/or a CIEy colorcoordinate of between 0.00 and 0.45, preferably between 0.01 and 0.30,more preferably between 0.02 and 0.20 or even more preferably between0.03 and 0.15 or even between 0.04 and 0.10.

In one embodiment of the invention, the second TADF material S^(B)exhibits an emission maximum λ_(max) ^(PMMA)(S^(B)) and the first TADFmaterial E^(B) exhibits an emission maximum λ_(max) ^(PMMA)(E^(B)),wherein 500 nm≥λ_(max) ^(PMMA)(S^(B))>λ_(max) ^(PMMA)(E^(B)).

In a more preferred embodiment, the second TADF material S^(B) exhibitsan emission maximum λ_(max) ^(PMMA)(S^(B)) and the first TADF materialE^(B) exhibits an emission maximum λ_(max) ^(PMMA)(E^(B)), wherein 480nm≥λ_(max) ^(PMMA)(S^(B))>λ_(max) ^(PMMA)(E^(B)).

In a preferred embodiment, the first TADF material E^(B) exhibits anemission maximum λ_(max) ^(PMMA)(E^(B)) in the range of from 450 to 470nm (i.e., 470 nm≥λ_(max) ^(PMMA)(E^(B))≥450 nm).

In a preferred embodiment, the second TADF material S^(B) exhibits anemission maximum λ_(max) ^(PMMA)(S^(B)), the first TADF material E^(B)exhibits an emission maximum λ_(max) ^(PMMA)(E^(B)) and the deviceexhibits an emission maximum λ_(max)(D), wherein λ_(max)^(PMMA)(S^(B))>λ_(max)(D)≥λ_(max) ^(PMMA)(E^(B)).

Due to the layer design the emission of the device can be even furthershifted to the blue. Accordingly in a further embodiment of theinvention, the second TADF material S^(B) exhibits an emission maximumλ_(max) ^(PMMA)(S^(B)), the first TADF material E^(B) exhibits anemission maximum λ_(max) ^(PMMA)(E^(B)) and the device exhibits anemission maximum λ_(max)(D), wherein λ_(max) ^(PMMA)(S^(B))>λ_(max)^(PMMA)(E^(B))>λ_(max)(D).

In a preferred embodiment, the first TADF material E^(B) and the secondTADF material S^(B) are independently from another both chosen frommolecules of a structure of Formula I

-   -   wherein    -   n is at each occurrence independently from another 1 or 2;    -   X is at each occurrence independently from another selected CN        or CF₃,    -   Z is at each occurrence independently from another selected from        the group consisting of a direct bond, CR³R⁴, C═CR³R⁴, C═O,        C═NR³, NR³, O, SiR³R⁴, S, S(O) and S(O)₂;

Ar^(EWG) is at each occurrence independently from another a structureaccording to one of Formulas IIa to IIi

wherein # represents the binding site of the single bond linkingAr^(EWG) to the substituted central phenyl ring of Formula I;

R¹ is at each occurrence independently from another selected from thegroup consisting of hydrogen, deuterium, C₁-C₅-alkyl, wherein one ormore hydrogen atoms are optionally substituted by deuterium, andC₆-C₁₈-aryl, which is optionally substituted with one or moresubstituents R⁶;

R² is at each occurrence independently from another selected from thegroup consisting of hydrogen, deuterium, C₁-C₅-alkyl, wherein one ormore hydrogen atoms are optionally substituted by deuterium, andC₆-C₁₈-aryl, which is optionally substituted with one or moresubstituents R⁶;

R^(a), R³ and R⁴ is at each occurrence independently from anotherselected from the group consisting of hydrogen, deuterium, N(R⁵)₂, OR⁵,SR⁵, Si(R⁵)₃, CF₃, CN, F, C₁-C₄₀-alkyl which is optionally substitutedwith one or more substituents R⁵ and wherein one or more non-adjacentCH₂-groups are optionally substituted by R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂,Sn(R⁵)₂, C═O, C═S, C═Se, C═NR⁵, P(═O)(R⁵), SO, SO₂, NR⁵, O, S or CONR⁵;

C₁-C₄₀-thioalkoxy which is optionally substituted with one or moresubstituents R⁵ and wherein one or more non-adjacent CH₂-groups areoptionally substituted by R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂, Sn(R⁵)₂, C═O,C═S, C═Se, C═NR⁵, P(═O)(R⁵), SO, SO₂, NR⁵, O, S or CONR⁵; and

C₆-C₆₀-aryl which is optionally substituted with one or moresubstituents R⁵; C₃-C₅₇-heteroaryl which is optionally substituted withone or more substituents R⁵;

R⁵ is at each occurrence independently from another selected from thegroup consisting of hydrogen, deuterium, N(R⁶)₂, OR⁶, SR⁶, Si(R⁶)₃, CF₃,CN, F, C₁-C₄₀-alkyl which is optionally substituted with one or moresubstituents R⁶ and wherein one or more non-adjacent CH₂-groups areoptionally substituted by R⁶C═CR⁶, C≡C, Si(R⁶)₂, Ge(R⁶)₂, Sn(R⁶)₂, C═O,C═S, C═Se, C═NR⁶, P(═O)(R⁶), SO, SO₂, NR⁶, O, S or CONR⁶,

C₆-C₆₀-aryl which is optionally substituted with one or moresubstituents R⁶; and C₃-C₅₇-heteroaryl which is optionally substitutedwith one or more substituents R⁶;

R⁶ is at each occurrence independently from another selected from thegroup consisting of hydrogen, deuterium, OPh,CF₃, CN, F,

C₁-C₅-alkyl, wherein one or more hydrogen atoms are optionally,independently from each other substituted by deuterium, CN, CF₃, or F;C₁-C₅-alkoxy,

wherein one or more hydrogen atoms are optionally, independently fromeach other substituted by deuterium, CN, CF₃, or F;

C₁-C₅-thioalkoxy, wherein one or more hydrogen atoms are optionally,independently from each other substituted by deuterium, CN, CF₃, or F;

C₆-C₁₈-aryl which is optionally substituted with one or more C₁-C₅-alkylsubstituents;

C₃-C₁₇-heteroaryl which is optionally substituted with one or moreC₁-C₅-alkyl substituents;

N(C₆-C₁₈-aryl)₂,

N(C₃-C₁₇-heteroaryl)₂, and

N(C₃-C₁₇-heteroaryl)(C₆-C₁₈-aryl),

R^(d) is at each occurrence independently from another selected from thegroup consisting of hydrogen, deuterium, N(R⁵)₂, OR⁵, SR⁵, Si(R⁵)₃, CF₃,CN, F,

C₁-C₄₀-alkyl which is optionally substituted with one or moresubstituents R⁵ and wherein one or more non-adjacent CH₂-groups areoptionally substituted by

R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂, Sn(R⁵)₂, C═O, C═S, C═Se, C═NR⁵,P(═O)(R⁵), SO, SO₂, NR⁵, O, S or CONR⁵,

C₁-C₄₀-thioalkoxy which is optionally substituted with one or moresubstituents R⁵ and wherein one or more non-adjacent CH₂-groups areoptionally substituted by R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂, Sn(R⁵)₂, C═O,C═S, C═Se, C═NR⁵, P(═O)(R⁵), SO, SO₂, NR⁵, O, S or CONR⁵, and

C₆-C₆₀-aryl which is optionally substituted with one or moresubstituents R⁵; C₃-C₅₇-heteroaryl which is optionally substituted withone or more substituents

wherein the substituents R^(a), R³, R⁴ or R⁵ independently from eachother optionally may form a mono- or polycyclic, aliphatic, aromaticand/or benzo-fused ring system with one or more substituents R^(a), R³,R⁴ or R⁵ and

wherein the one or more substituents R^(d) independently from each otheroptionally may form a mono- or polycyclic, aliphatic, aromatic and/orbenzo-fused ring system with one or more substituents R^(d).

According to the invention, the substituents R^(a), R³, R⁴ or R⁵ at eacheach occurrence independently from each other may optionally form amono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring systemwith one or more substituents R^(a), R³, R⁴ or R⁵.

According to the invention, the substituents R^(d) at each eachoccurrence independently from each other may optionally form a mono- orpolycyclic, aliphatic, aromatic and/or benzo-fused ring system with oneor more other substituents R^(d).

In a preferred embodiment of the invention, the first TADF materialE^(B) and the second TADF material S^(B) both bear the same structureaccording to Formula I structurally only differing in one or more ofR^(a), R¹, R² and X. In other words, both TADF materials S^(B) and E^(B)may bear the same structure according to Formula I and differ in atleast one substituent chosen from the group consisting of R^(a), R¹, R²and X.

In a preferred embodiment of the invention, S^(B) and E^(B) comprise orconsist of the same structure according to Formula I and differ in oneor more substituents R^(a). In the following table, exemplarily S^(B)and E^(B) pairs according to this embodiment (each line representing anexemplified pair) are listed:

S^(B) E^(B)

wherein Ar^(EWG) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) bear the samestructure according to Formula IIa to Formula IIi and (only) differ inthe substitution pattern of the substituted central phenyl ring ofFormula I. Accordingly, In a preferred embodiment, S^(B) and E^(B)(only) differ in that residue X is defined differently. In anotherembodiment, S^(B) and E^(B) (only) differ in that residue n is defineddifferently. In another embodiment, S^(B) and E^(B) (only) differ inthat residues n and X are each defined differently. It will beunderstood that the further residues may be defined as above and may bein particular defined according to any exemplified structures and/orembodiments.

In a particularly preferred embodiment of the invention, Z is a directbond at each occurrence. Particularly preferred, Z is a direct bond ateach occurrence in both TADF materials S^(B) and E^(B).

In one embodiment of the invention, R^(a) is at each occurrenceindependently from another selected from the group consisting ofhydrogen, deuterium, Me, ^(i)Pr, ^(t)Bu, CN, CF₃,

Ph, which is optionally substituted with one or more substituentsindependently from each other selected from the group consisting of Me,^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

pyridinyl, which is optionally substituted with one or more substituentsindependently from each other selected from the group consisting of Me,^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

pyrimidinyl, which is optionally substituted with one or moresubstituents independently from each other selected from the groupconsisting of Me, ^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

carbazolyl, which is optionally substituted with one or moresubstituents independently from each other selected from the groupconsisting of Me, ^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

triazinyl, which is optionally substituted with one or more substituentsindependently from each other selected from the group consisting of Me,^(i)Pr, ^(t)Bu, CN, CF₃ and Ph; and N(Ph)₂.

In one embodiment of the invention, R^(d) is at each occurrenceindependently from another selected from the group consisting ofhydrogen, deuterium, Me, ^(i)Pr, ^(t)Bu, CN, CF₃,

Ph, which is optionally substituted with one or more substituentsindependently from each other selected from the group consisting of Me,^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

pyridinyl, which is optionally substituted with one or more substituentsindependently from each other selected from the group consisting of Me,^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

pyrimidinyl, which is optionally substituted with one or moresubstituents independently from each other selected from the groupconsisting of Me, ^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

carbazolyl, which is optionally substituted with one or moresubstituents independently from each other selected from the groupconsisting of Me, ^(i)Pr, ^(t)Bu, CN, CF₃ and Ph;

triazinyl, which is optionally substituted with one or more substituentsindependently from each other selected from the group consisting of Me,^(i)Pr, ^(t)Bu, CN, CF₃ and Ph; and N(Ph)₂.

In a preferred embodiment, X is CN. Preferably, X may be CN in bothoccurrence in both TADF materials S^(B) and E^(B).

In one embodiment of the invention, the TADF materials S^(B) and E^(B)are independently from another both chosen from molecules of a structureof Formula III:

wherein R^(a), X and R¹ are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula IIIa:

wherein R^(a), X and R¹ are defined as above. In one embodiment of theinvention, S^(B) and E^(B) are independently from another both chosenfrom molecules of a structure of Formula IIIb:

wherein R^(a) and R¹ are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula IV:

wherein R^(a), R¹ and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula IVa:

wherein R^(a), R¹ and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula IVb:

wherein R^(a) and R¹ are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula V:

wherein R^(a), R¹ and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula Va:

wherein R^(a), R¹ and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula Vb:

wherein R^(a) and R¹ are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VI:

wherein R^(a), R¹ and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VIa:

wherein R^(a), R¹ and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VIb:

wherein R^(a) and R¹ are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VII:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VIIa:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VIIb:

wherein R^(a) is defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VIII:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VIIIa:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula VIIIb:

wherein R^(a) is defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula IX:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula IXa:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula IXb:

wherein R^(a) is defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula X:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula Xa:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula Xb:

wherein R^(a) is defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula XI:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula XIa:

wherein R^(a) and X are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula XIb:

wherein R^(a) is defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula XII:

wherein R^(a), X and R^(d) are defined as above.

In one embodiment of the invention, S^(B) and E^(B) are independentlyfrom another both chosen from molecules of a structure of Formula XIIa:

wherein R^(a), X and R^(d) are defined as above.

The synthesis of the molecules of a structure of Formula I can beaccomplished via standard reactions and reaction conditions known to theskilled artesian. Typically, in a first step a coupling reaction,preferably a palladium catalyzed coupling reaction, is performed.

E1 can be any boronic acid (R^(b)═H) or an equivalent boronic acid ester(R^(b)═alkyl or aryl), in particular two R^(B) form a ring to give e.g.boronic acid pinacol esters, of fluoro-(trifluoromethyl)phenyl,difluoro-(trifluoromethyl)phenyl, fluoro-(cyano)phenyl ordifluoro-(cyano)phenyl. As second reactant E2 preferably Ar^(EWG)—Br isused. Reaction conditions of such palladium catalyzed coupling reactionsare known the person skilled in the art, e.g. from WO 2017/005699, andit is known that the reacting groups of E1 and E2 can be interchanged tooptimize the reaction yields.

In a second step, the molecules according to Formular I are obtained viathe reaction of a nitrogen heterocycle in a nucleophilic aromaticsubstitution with the aryl halide, preferably aryl fluoride, or aryldihalide, preferably aryl difluoride, E3. Typical conditions include theuse of a base, such as tribasic potassium phosphate or sodium hydride,for example, in an aprotic polar solvent, such as dimethyl sulfoxide(DMSO) or N,N-dimethylformamide (DMF), for example.

In particular, the donor molecule E6 is a 3,6-substituted carbazole(e.g., 3,6-dimethylcarbazole, 3,6 diphenylcarbazole,3,6-di-tert-butylcarbazole), a 2,7-substituted carbazole (e.g., 2,7dimethylcarbazole, 2,7-diphenylcarbazole, 2,7-di-tert-butylcarbazole), a1,8-substituted carbazole (e.g., 1,8-dimethylcarbazole,1,8-diphenylcarbazole, 1,8-di-tert-butylcarbazole), a 1 substitutedcarbazole (e.g., 1-methylcarbazole, 1-phenylcarbazole,1-tert-butylcarbazole), a 2 substituted carbazole (e.g.,2-methylcarbazole, 2-phenylcarbazole, 2-tert-butylcarbazole), or a 3substituted carbazole (e.g., 3-methylcarbazole, 3-phenylcarbazole,3-tert-butylcarbazole).

Alternatively, a halogen-substituted carbazole, particularly3-bromocarbazole, can be used as E6.

In a subsequent reaction a boronic acid ester functional group orboronic acid functional group may be exemplarily introduced at theposition of the one or more halogen substituents, which was introducedvia E6, to yield the corresponding carbazol-3-ylboronic acid ester orcarbazol-3-ylboronic acid, e.g., via the reaction withbis(pinacolato)diboron (CAS No. 73183-34-3). Subsequently, one or moresubstituents R^(a) may be introduced in place of the boronic acid estergroup or the boronic acid group via a coupling reaction with thecorresponding halogenated reactant R^(a)-Hal, preferably R^(a)—C1 andR^(a)—Br.

Alternatively, one or more substituents R^(a) may be introduced at theposition of the one or more halogen substituents, which was introducedvia D-H, via the reaction with a boronic acid of the substituent R^(a)[R^(a)—B(OH)₂] or a corresponding boronic acid ester.

An alternative synthesis route comprises the introduction of a nitrogenheterocycle via copper-or palladium-catalyzed coupling to an aryl halideor aryl pseudohalide, preferably an aryl bromide, an aryl iodide, aryltriflate or an aryl tosylate.

As used throughout the present application, the terms “aryl” and“aromatic” may be understood in the broadest sense as any mono-, bi- orpolycyclic aromatic moieties. If not otherwise indicated, an aryl mayalso be optionally substituted by one or more substituents which areexemplified further throughout the present application. Accordingly, theterm “arylene” refers to a divalent residue that bears two binding sitesto other molecular structures and thereby serving as a linker structure.As used throughout the present application, the terms “heteroaryl” and“heteroaromatic” may be understood in the broadest sense as any mono-,bi- or polycyclic heteroaromatic moieties that include at least oneheteroatom, in particular which bear from one to three heteroatoms peraromatic ring. Exemplarily, a heteroaromatic compound may be pyrrole,furan, thiophene, imidazole, oxazole, thiazole, triazole, pyrazole,pyridine, pyrazine and pyrimidine, and the like. If not otherwiseindicated, a heteroaryl may also be optionally substituted by one ormore substituents which are exemplified further throughout the presentapplication. Accordingly, the term “heteroarylene” refers to a divalentresidue that bears two binding sites to other molecular structures andthereby serving as a linker structure.

As used throughout the present application, the term “alkyl” may beunderstood in the broadest sense as both, linear or branched chain alkylresidue. Preferred alkyl residues are those containing from one tofifteen carbon atoms. Exemplarily, an alkyl residue may be methyl,ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Ifnot otherwise indicated, an alkyl may also be optionally substituted byone or more substituents which are exemplified further throughout thepresent application. Accordingly, the term “alkylene” refers to adivalent residue that bears two binding sites to other molecularstructures and thereby serving as a linker structure.

If not otherwise indicated, as used herein, in particular in the contextof aryl, arylene, heteroaryl, alkyl and the like, the term “substituted”may be understood in the broadest sense. Preferably, such substitutionmeans a residue selected from the group consisting of C₁-C₂₀-alkyl,C₇-C₁₉-alkaryl, and C₆-C₁₈-aryl. Accordingly, preferably, no chargedmoiety, more preferably no functional group is present in suchsubstitution.

It will be noticed that hydrogen can, at each occurrence, be replaced bydeuterium.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. The layers in the context ofthe present invention, including the light-emitting layer B, mayoptionally be prepared by means of liquid processing (also designated as“film processing”, “fluid processing”, “solution processing” or “solventprocessing”). This means that the components comprised in the respectivelayer are applied to the surface of a part of a device in liquid state.Preferably, the layers in the context of the present invention,including the light-emitting layer B, may be prepared by means ofspin-coating. This method well-known to those skilled in the art allowsobtaining thin and (essentially) homogeneous layers.

Alternatively, the layers in the context of the present invention,including the light-emitting layer B, may be prepared by other methodsbased on liquid processing such as, e.g., casting (e.g., drop-casting)and rolling methods, and printing methods (e.g., inkjet printing,gravure printing, blade coating). This may optionally be carried out inan inert atmosphere (e.g., in a nitrogen atmosphere).

In another preferred embodiment, the layers in the context of thepresent invention may be prepared by any other method known in the art,including but not limited to vacuum processing methods well-known tothose skilled in the art such as, e.g., thermal (co-)evaporation,organic vapor phase deposition (OVPD), and deposition by organic vaporjet printing (OVJP).

When preparing layers by means of liquid processing, the solutionsincluding the components of the layers (i.e., with respect to thelight-emitting layer B of the present invention, at least one hostcompound H^(B) and, typically, at least one first TADF material E^(B),at least one second TADF material S^(B) and optionally one or more otherhost compounds H^(B2)) may further comprise a volatile organic solvent.Such volatile organic solvent may optionally be one selected from thegroup consisting of tetrahydrofuran, dioxane, chlorobenzene, diethyleneglycol diethyl ether, 2-(2-ethoxyethoxy)ethanol, gamma-butyrolactone,N-methyl pyrrolidinon, ethoxyethanol, xylene, toluene, anisole,phenetol, acetonitrile, tetrahydrothiophene, benzonitrile, pyridine,trihydrofuran, triarylamine, cyclohexanone, acetone, propylenecarbonate, ethyl acetate, benzene and PGMEA (propylen glycol monoethylether acetate). Also a combination of two or more solvents may be used.After applied in liquid state, the layer may subsequently be driedand/or hardened by any means of the art, exemplarily at ambientconditions, at increased temperature (e.g., about 50° C. or about 60°C.) or at diminished pressure.

Optionally, an organic electroluminescent device (e.g., an OLED) mayexemplarily be an essentially white organic electroluminescent device ora blue organic electroluminescent device. Exemplarily such white organicelectroluminescent device may comprise at least one (deep) blue emittercompound (e.g., TADF material E^(B)) and one or more emitter compoundsemitting green and/or red light. Then, there may also optionally beenergy transmittance between two or more compounds as described above.

The organic electroluminescent device as a whole may also form a thinlayer of a thickness of not more than 5 mm, more than 2 mm, more than 1mm, more than 0.5 mm, more than 0.25 mm, more than 100 μm, or more than10 μm.

An organic electroluminescent device (e.g., an OLED) may be asmall-sized (e.g., having a surface not larger than 5 mm², or even notlarger than 1 mm²), medium-sized (e.g., having a surface in the range of0.5 to 20 cm²), or a large-sized (e.g., having a surface larger than 20cm²). An organic electroluminescent device (e.g., an OLED) according tothe present invention may optionally be used for generating screens, aslarge-area illuminating device, as luminescent wallpaper, luminescentwindow frame or glass, luminescent label, luminescent poser or flexiblescreen or display. Next to the common uses, an organicelectroluminescent device (e.g., an OLED) may exemplarily also be usedas luminescent films, “smart packaging” labels, or innovative designelements. Further they are usable for cell detection and examination(e.g., as bio labelling).

One of the main purposes of an organic electroluminescent device is thegeneration of light. Thus, the present invention further relates to amethod for generating light of a desired wavelength range, comprisingthe step of providing an organic electroluminescent device according toany the present invention.

Accordingly, a further aspect of the present invention relates to amethod for generating light of a desired wavelength range, comprisingthe steps of

-   (i) providing an organic electroluminescent device according to the    present invention; and-   (ii) applying an electrical current to said organic    electroluminescent device.

A further aspect of the present invention relates to a process of makingthe organic electroluminescent devices by assembling the elementsdescribed above. The present invention also relates to a method forgenerating blue, green, yellow, orange, red or white light, inparticular blue or white light by using said organic electroluminescentdevice.

The FIGURE and Examples and claims further illustrate the invention.

BRIEF DESCRIPTION OF THE FIGURE

The FIGURE shows an emission spectrum of device C2 at 7V.

EXAMPLES

Cyclic Voltammetry

Cyclic voltammograms of solutions having concentration of 10-3 mol/l ofthe organic molecules in dichloromethane or a suitable solvent and asuitable supporting electrolyte (e.g. 0.1 mol/l of tetrabutylammoniumhexafluorophosphate) are measured. The measurements are conducted atroom temperature and under nitrogen atmosphere with a three-electrodeassembly (Working and counter electrodes: Pt wire, reference electrode:Pt wire) and calibrated using FeCp_(2/)FeCp₂ ⁺ as internal standard.HOMO data was corrected using ferrocene as internal standard againstSCE.

Density Functional Theory Calculation

Molecular structures are optimized employing the BP86 functional and theresolution of identity approach (RI). Excitation energies are calculatedusing the (BP86) optimized structures employing Time-Dependent DFT(TD-DFT) methods. Orbital and excited state energies are calculated withthe B3LYP functional. Def2-SVP basis sets (and a m4-grid for numericalintegration were used. The Turbomole program package was used for allcalculations.

Photophysical Measurements

Sample pretreatment: Spin-coating

Apparatus: Spin150, SPS euro.

The sample concentration is 10 mg/ml, dissolved in a suitable solvent.Program: 1) 3 s at 400 U/min, 20 s at 1000 U/min at 1000 Upm/s. 3) 10 sat 4000 U/min at 1000 Upm/s. After coating, the films are tried at 70°C. for 1 min.

Photoluminescence spectroscopy and TCSPC (Time-correlated single-photoncounting)

Steady-state emission spectroscopy is recorded using a HoribaScientific, Modell FluoroMax-4 equipped with a 150 W Xenon-Arc lamp,excitation- and emissions monochromators and a Hamamatsu R928photomultiplier and a time-correlated single-photon counting option.Emissions and excitation spectra are corrected using standard correctionfits.

Excited state lifetimes are determined employing the same system usingthe TCSPC method with FM-2013 equipment and a Horiba Yvon TCSPC hub.

Excitation Sources:

NanoLED 370 (wavelength: 371 nm, puls duration: 1,1 ns)

NanoLED 290 (wavelength: 294 nm, puls duration: <1 ns)

SpectraLED 310 (wavelength: 314 nm)

SpectraLED 355 (wavelength: 355 nm).

Data analysis (exponential fit) was done using the software suiteDataStation and DAS6 analysis software. The fit is specified using thechi-squared-test.

Photoluminescence Quantum Yield Measurements

For photoluminescence quantum yield (PLQY) measurements an Absolute PLQuantum Yield Measurement C9920-O3G system (Hamamatsu Photonics) isused. Quantum yields and CIE coordinates were determined using thesoftware U6039-C₅ version 3.6.0.

Emission maxima are given in nm, quantum yields ϕ in % and CIEcoordinates as x,y values.

PLQY was determined using the following protocol:

-   -   1) Quality assurance: Anthracene in ethanol (known        concentration) is used as reference    -   2) Excitation wavelength: the absorption maximum of the organic        molecule is determined and the molecule is excited using this        wavelength    -   3) Measurement        -   Quantum yields are measured for sample of solutions or films            under nitrogen atmosphere. The yield is calculated using the            equation:

$\Phi_{PL} = {\frac{n_{photon},{emited}}{n_{photon},{absorbed}} = \frac{\int{{\frac{\lambda}{hc}\left\lbrack {{{Int}_{emitted}^{sample}(\lambda)} - {{Int}_{absorbed}^{sample}(\lambda)}} \right\rbrack}d\;\lambda}}{\int{{\frac{\lambda}{hc}\left\lbrack {{{Int}_{emitted}^{reference}(\lambda)} - {{Int}_{absorbed}^{reference}(\lambda)}} \right\rbrack}d\;\lambda}}}$

-   -   -   wherein n_(photon) denotes the photon count and Int. is the            intensity.

Production and Characterization of Organic Electroluminescence Devices

Via vacuum-deposition methods OLED devices comprising organic moleculesaccording to the invention can be produced. If a layer contains morethan one compound, the weight-percentage of one or more compounds isgiven in %. The total weight-percentage values amount to 100%, thus if avalue is not given, the fraction of this compound equals to thedifference between the given values and 100%.

The not fully optimized OLEDs are characterized using standard methodsand measuring electroluminescence spectra, the external quantumefficiency (in %) in dependency on the intensity, calculated using thelight detected by the photodiode, and the current. The OLED devicelifetime is extracted from the change of the luminance during operationat constant current density. The LT50 value corresponds to the time,where the measured luminance decreased to 50% of the initial luminance,analogously LT80 corresponds to the time point, at which the measuredluminance decreased to 80% of the initial luminance, LT97 to the timepoint, at which the measured luminance decreased to 97% of the initialluminance etc.

Accelerated lifetime measurements are performed (e.g. applying increasedcurrent densities). Exemplarily LT80 values at 500 cd/m² are determinedusing the following equation:

${{LT}\; 80\left( {500\mspace{14mu}\frac{{cd}^{2}}{m^{2}}} \right)} = {{LT}\; 80\left( L_{0} \right)\left( \frac{L_{0}}{500\mspace{14mu}\frac{{cd}^{2}}{m^{2}}} \right)^{1.6}}$

wherein L₀ denotes the initial luminance at the applied current density.

The values correspond to the average of several pixels (typically two toeight), the standard deviation between these pixels is given. Figuresshow the data series for one OLED pixel.

Example D1 and Comparative Examples C1 and C2

HOMO [eV] LUMO [eV] S1 [eV] T1 [eV] mCBP −6.02 −2.34 2.95 TADF1 −6.16−3.16 2.94 2.83 TADF2 −6.07 −3.17 2.87 2.80 Layer Thickness D1 C1 C2 8100 nm Al Al Al 7  2 nm Liq Liq Liq 6  25 nm NBPhen NBPhen NBPhen 5  50nm TADF1 (15%): TADF2 (5%): T2T TADF1 (20%): TADF2 (5%): (15%): mCBPmCBP (80%) mCBP (80%) (80%) 4  10 nm mCBP mCBP mCBP 3  10 nm TCTA TCTATCTA 2  85 nm NPB NPB NPB (95 nm) 1 130 nm ITO ITO ITO substrate glassglass glass

Device D1 yielded an external quantum efficiency (EQE) at 1000 cd/m² of12.7±0.2%. The LT97 value at 730 cd/m² was determined to be 18 h fromaccelerated lifetime measurements. The emission maximum is at 469 nmwith a FWHM of 60 nm at 5 V. The corresponding ClEx value is 0.157 andClEy is 0.227.

Comparative device C1 comprises the same layer arrangement as device D1,except that the emitting layer contains only emitter TADF2 and TADF1 isreplaced by T2T. The EQE at 1000 cd/m² is significantly reduced to8.7±0.1% and the lifetime is shortened (LT97 at 730 cd/m²=11h). Theemission maximum is red-shifted at 472 nm with a FWHM of 64 nm at 5 V.The corresponding ClEx value is 0.162 and ClEy is 0.237.

Comparative device C2 comprises an emitting layer containing only TADF1as emitter. The EQE at 1000 cd/m² is comparable to D1 at 12.3±0.2%, butthe lifetime is significantly shortened (LT97 at 730 cd/m²=6 h). Theemission maximum appears again red-shifted at 473 nm with a FWHM of 61nm at 5 V. The corresponding ClEx value is 0.148 and ClEy is 0.207. Thelowered ClEy coordinate can be attributed to a shoulder at around 410 nmin the spectrum attributable to the emission of NBPhen (Figure)indicating a less well balanced charge distribution within the EML.

The invention claimed is:
 1. An organic electroluminescent devicecomprising a light-emitting layer B comprising: (i) a host materialH^(B), which has a lowermost excited singlet state energy level S1^(H)and a lowermost excited triplet state energy level T1^(H); (ii) a firstthermally activated delayed fluorescence (TADF) material E^(B), whichhas a lowermost excited singlet state energy level S1^(E) and alowermost excited triplet state energy level T1^(E); and (iii) a secondTADF material S^(B), which has a lowermost excited singlet state energylevel S1^(S) and a lowermost excited triplet state energy level T1^(S),wherein E^(B) transfers energy to S^(B) and S^(B) emits thermallyactivated delayed fluorescence with an emission maximum between 420 and500 nm; and wherein the relations expressed by the following formulas(1) to (4) apply:S1^(H) >S1^(E)  (1)S1^(H) >S1^(S)  (2)S1^(E) >S1^(S)  (3)T1^(H) >T1^(S)  (4).
 2. The organic electroluminescent device accordingto claim 1, wherein said organic electroluminescent device is a deviceselected from the group consisting of an organic light emitting diode, alight emitting electrochemical cell, and a light-emitting transistor. 3.The organic electroluminescent device according to claim 1, wherein thefirst TADF material E^(B) is an organic TADF emitter.
 4. The organicelectroluminescent device according to claim 1, wherein the second TADFmaterial S^(B) is an organic TADF emitter.
 5. The organicelectroluminescent device according to claim 1, wherein the deviceexhibits an emission maximum λ_(max)(D) of 440 to 470 nm.
 6. The organicelectroluminescent device according to claim 1, wherein thelight-emitting layer B comprises: (i) 5-98% by weight of the hostcompound H^(B); (ii) 1-50% by weight of the first TADF material E^(B);and (iii) 1-50% by weight of the second TADF material S^(B); andoptionally (iv) 0-93% by weight of one or more further host compoundsH^(B2) differing from H^(B); and optionally (v) 0-93% by weight of oneor more solvents.
 7. The organic electroluminescent device according toclaim 1, wherein the second TADF material S^(B) exhibits an emissionmaximum λ_(max) ^(PMMA)(S^(B)) and the first TADF material E^(B)exhibits an emission maximum λ_(max) ^(PMMA)(E^(B)), wherein500 nm≥λ_(max) ^(PMMA)(S ^(B))>λ_(max) ^(PMMA)(E ^(B)).
 8. The organicelectroluminescent device according to claim 1, wherein the first TADFmaterial E^(B) exhibits an emission maximum λ_(max) ^(PMMA)(E^(B)) inthe range of from 450 to 470 nm.
 9. The organic electroluminescentdevice according to claim 1, wherein the second TADF material S^(B)exhibits an emission maximum λ_(max) ^(PMMA)(S^(B)), the first TADFmaterial E^(B) exhibits an emission maximum λ_(max) ^(PMMA)(E^(B)) andthe device exhibits an emission maximum λ_(max)(D), whereinλ_(max) ^(PMMA)(S ^(B))>λ_(max)(D)≥λ_(max) ^(PMMA)(E ^(B)).
 10. Theorganic electroluminescent device according to claim 1, whereinT1^(E)>T1^(S).
 11. The organic electroluminescent device according toclaim 1, whereinS1^(E) >S1^(S) ≥T1^(E) >T1^(S) andS1^(E) −T1^(S)≤0.4 eV.
 12. The organic electroluminescent deviceaccording to claim 1, wherein first TADF material E^(B) and the secondTADF material S^(B) are independently from another both chosen frommolecules of a structure of Formula I

wherein n is at each occurrence independently from another 1 or 2; X isat each occurrence independently from another CN or CF₃; Z is at eachoccurrence independently from another selected from the group consistingof a direct bond, CR³R⁴, C═CR³R⁴, C═O, C═NR³, NR³, O, SiR³R⁴, S, S(O),and S(O)₂; Ar^(EwG) is at each occurrence independently from another astructure according to one of Formulas IIa to IIi

wherein # represents the binding site of the single bond linkingAr^(EWG) to the substituted central phenyl ring of Formula I; R¹ is ateach occurrence independently from another selected from the groupconsisting of hydrogen, deuterium, C₁-C₅-alkyl, wherein one or morehydrogen atoms are optionally substituted by deuterium, and C₆-C₁₈-aryl,which is optionally substituted with one or more substituents R⁶; R² isat each occurrence independently from another selected from the groupconsisting of hydrogen, deuterium, C₁-C₅-alkyl, wherein one or morehydrogen atoms are optionally substituted by deuterium, and C₆-C₁₈-aryl,which is optionally substituted with one or more substituents R⁶; R^(a),R³, and R⁴ is at each occurrence independently from another selectedfrom the group consisting of hydrogen, deuterium, N(R⁵)₂, OR⁵, SR⁵,Si(R⁵)₃, CF₃, CN, F, C₁-C₄₀-alkyl, which is optionally substituted withone or more substituents R⁵ and wherein one or more non-adjacentCH₂-groups are optionally substituted by R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂,Sn(R⁵)₂, C═O, C═S, C═Se, C═NR⁵, P(═O)(R⁵), SO, SO₂, NR⁵, O, S, or CONR⁵;C₁-C₄₀-thioalkoxy, which is optionally substituted with one or moresubstituents R⁵ and wherein one or more non-adjacent CH₂-groups areoptionally substituted by R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂, Sn(R⁵)₂, C═O,C═S, C═Se, C═NR⁵, P(═O)(R⁵), SO, SO₂, NR⁵, O, S, or CONR⁵; C₆-C₆₀-aryl,which is optionally substituted with one or more substituents R⁵; andC₃-C₅₇-heteroaryl, which is optionally substituted with one or moresubstituents R⁵; R⁵ is at each occurrence independently from anotherselected from the group consisting of hydrogen, deuterium, N(R⁶)₂, OR⁶,SR⁶, Si(R⁶)₃, CF₃, CN, F, C₁-C₄₀-alkyl, which is optionally substitutedwith one or more substituents R⁶ and wherein one or more non-adjacentCH₂-groups are optionally substituted by R⁶C═CR⁶, C≡C, Si(R⁶)₂, Ge(R⁶)₂,Sn(R⁶)₂, C═O, C═S, C═Se, C═NR⁶, P(═O)(R⁶), SO, SO₂, NR⁶, O, S, or CONR⁶;C₆-C₆₀-aryl, which is optionally substituted with one or moresubstituents R⁶; and C₃-C₅₇-heteroaryl, which is optionally substitutedwith one or more substituents R⁶; R⁶ is at each occurrence independentlyfrom another selected from the group consisting of hydrogen, deuterium,OPh,CF₃, CN, F, C₁-C₅-alkyl, wherein one or more hydrogen atoms areoptionally, independently from each other, substituted by deuterium, CN,CF₃, or F; C₁-C₅-alkoxy, wherein one or more hydrogen atoms areoptionally, independently from each other, substituted by deuterium, CN,CF₃, or F; C₁-C₅-thioalkoxy, wherein one or more hydrogen atoms areoptionally, independently from each other, substituted by deuterium, CN,CF₃, or F; C₆-C₁₈-aryl, which is optionally substituted with one or moreC₁-C₅-alkyl substituents; C₃-C₁₇-heteroaryl, which is optionallysubstituted with one or more C₁-C₅-alkyl substituents; N(C₆-C₁₈-aryl)₂;N(C₃-C₁₇-heteroaryl)₂; and N(C₃-C₁₇-heteroaryl)(C₆-C₁₈-aryl); R^(d) isat each occurrence independently from another selected from the groupconsisting of hydrogen, deuterium, N(R⁵)₂, OR⁵, SR⁵, Si(R⁵)₃, CF₃, CN,F, C₁-C₄₀-alkyl, which is optionally substituted with one or moresubstituents R⁵ and wherein one or more non-adjacent CH₂-groups areoptionally substituted by R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂, Sn(R⁵)₂, C═O,C═S, C═Se, C═NR⁵, P(═O)(R⁵), SO, SO₂, NR⁵, O, S, or CONR⁵;C₁-C₄₀-thioalkoxy, which is optionally substituted with one or moresubstituents R⁵ and wherein one or more non-adjacent CH₂-groups areoptionally substituted by R⁵C═CR⁵, C≡C, Si(R⁵)₂, Ge(R⁵)₂, Sn(R⁵)₂, C═O,C═S, C═Se, C═NR⁵, P(═O)(R⁵), SO, SO₂, NR⁵, O, S, or CONR⁵; andC₆-C₆₀-aryl, which is optionally substituted with one or moresubstituents R⁵; and C₃-C₅₇-heteroaryl which is optionally substitutedwith one or more substituents R⁵; wherein the substituents R^(a), R³,R⁴, or R⁵ independently from each other optionally may form a mono- orpolycyclic, aliphatic, aromatic, and/or benzo-fused ring system with oneor more substituents R^(a), R³, R⁴, or R⁵, and wherein the one or moresubstituents R^(d) independently from each other optionally may form amono- or polycyclic, aliphatic, aromatic, and/or benzo-fused ring systemwith one or more substituents R^(d).
 13. The organic electroluminescentdevice according to claim 12, wherein the first TADF material E^(B) andthe second TADF material S^(B) both bear the same structure according toFormula I structurally only differing in one or more of R^(a), R¹, R²,and X.
 14. The organic electroluminescent device according to claim 12,wherein Z is a direct bond at each occurrence.
 15. The organicelectroluminescent device according to claim 12, wherein R^(a) is ateach occurrence independently from another selected from the groupconsisting of hydrogen, deuterium, Me, ^(i)Pr, ^(t)Bu, CN, CF₃, Ph,which is optionally substituted with one or more substituentsindependently from each other selected from the group consisting of Me,^(i)Pr, ^(t)Bu, CN, CF₃, and Ph; pyridinyl, which is optionallysubstituted with one or more substituents independently from each otherselected from the group consisting of Me, ^(i)Pr, ^(t)Bu, CN, CF₃, andPh; pyrimidinyl, which is optionally substituted with one or moresubstituents independently from each other selected from the groupconsisting of Me, ^(i)Pr, ^(t)Bu, CN, CF₃, and Ph; carbazolyl, which isoptionally substituted with one or more substituents independently fromeach other selected from the group consisting of Me, ^(i)Pr, ^(t)Bu, CN,CF₃, and Ph; triazinyl, which is optionally substituted with one or moresubstituents independently from each other selected from the groupconsisting of Me, ^(i)Pr, ^(t)Bu, CN, CF₃, and Ph; and N(Ph)₂.
 16. Theorganic electroluminescent device according to claim 1, wherein thesecond TADF material S^(B) exhibits an emission maximum λ_(max)^(PMMA)(S^(B)) and the first TADF material E^(B) exhibits an emissionmaximum λ_(max) ^(PMMA)(E^(B)), wherein480 nm λ_(max) ^(PMMA)(S ^(B))>λ_(max) ^(PMMA)(E ^(B)).